Supernucleation dominates lignin/poly(ethylene oxide) rystallization kinetics

Autores
Taverna, María E.; Altorbaq, Abdullah S.; Kumar, Sanat K.; Olmedo Martínez, Jorge L.; Busatto, Carlos Alberto; Zubitur, Manuela; Mugica, Agurtzane; Nicolau, Verónica V.; Estenoz, Diana; Müller, Alejandro J.
Año de publicación
2022
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed welldispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/ PEO) in the brush-controlled regime.
Fil: Taverna, María E. UNL - CONICET. INTEC - Universidad Tecnológica Nacional. Facultad Regional San Francisco. Departamento de Ingeniería Química, Grupo UTN GPol; Argentina.
Fil: Altorbaq, Abdullah S. Columbia University. Department of Chemical Engineering; USA
Fil: Kumar, Sanat K. Columbia University. Department of Chemical Engineering; USA.
Fil: Olmedo-Martínez, Jorge L. Basque Foundation for Science. IKERBASQUE; España.
Fil: Busatto, Carlos Alberto. UNL - CONICET. INTEC; Argentina
Fil: Zubitur, Manuela. University of the Basque Country UPV/EHU. Chemical and Environmental Engineering Department; España.
Fil: Mugica, Agurtzane. University of the Basque Country UPV/EHU. POLYMAT; España.
Fil: Nicolau, Verónica V. Universidad Tecnológica Nacional. Facultad Regional San Francisco. Departamento de Ingeniería Química, Grupo UTN GPol - CONICET; Argentina.
Fil: Estenoz, Diana. UNL - CONICET. INTEC; Argentina.
Fil: Alejandro J. Müller. Basque Foundation for Science. IKERBASQUE; España.
Peer Reviewed
Fuente
Macromolecules 2022 (55) 7663–767. (2022)
Materia
Lignin
Crystallization
Poly(ethylene oxide)
Nivel de accesibilidad
acceso abierto
Condiciones de uso
2024-04-03T20:15:26Z
Repositorio
Repositorio Institucional Abierto (UTN)
Institución
Universidad Tecnológica Nacional
OAI Identificador
oai:ria.utn.edu.ar:20.500.12272/10287
Acceder
id RIAUTN_7b81d01a72280fad32cd1a5fc4f3d95b
oai_identifier_str oai:ria.utn.edu.ar:20.500.12272/10287
network_acronym_str RIAUTN
repository_id_str a
network_name_str Repositorio Institucional Abierto (UTN)
spelling Supernucleation dominates lignin/poly(ethylene oxide) rystallization kineticsTaverna, María E.Altorbaq, Abdullah S.Kumar, Sanat K.Olmedo Martínez, Jorge L.Busatto, Carlos AlbertoZubitur, ManuelaMugica, AgurtzaneNicolau, Verónica V.Estenoz, DianaMüller, Alejandro J.LigninCrystallizationPoly(ethylene oxide)The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed welldispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/ PEO) in the brush-controlled regime.Fil: Taverna, María E. UNL - CONICET. INTEC - Universidad Tecnológica Nacional. Facultad Regional San Francisco. Departamento de Ingeniería Química, Grupo UTN GPol; Argentina.Fil: Altorbaq, Abdullah S. Columbia University. Department of Chemical Engineering; USAFil: Kumar, Sanat K. Columbia University. Department of Chemical Engineering; USA.Fil: Olmedo-Martínez, Jorge L. Basque Foundation for Science. IKERBASQUE; España.Fil: Busatto, Carlos Alberto. UNL - CONICET. INTEC; ArgentinaFil: Zubitur, Manuela. University of the Basque Country UPV/EHU. Chemical and Environmental Engineering Department; España.Fil: Mugica, Agurtzane. University of the Basque Country UPV/EHU. POLYMAT; España.Fil: Nicolau, Verónica V. Universidad Tecnológica Nacional. Facultad Regional San Francisco. Departamento de Ingeniería Química, Grupo UTN GPol - CONICET; Argentina.Fil: Estenoz, Diana. UNL - CONICET. INTEC; Argentina.Fil: Alejandro J. Müller. Basque Foundation for Science. IKERBASQUE; España.Peer Reviewed2024-04-03T20:15:26Z2024-04-03T20:15:26Z2022-08info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articulopdfapplication/pdfMacromolecules 2022, 55, 17, 7663–7673 Publication Date:August 26, 2022 https://doi.org/10.1021/acs.macromol.2c0092515205835https://pubs.acs.org/doi/10.1021/acs.macromol.2c00925http://hdl.handle.net/20.500.12272/10287Macromolecules 2022 (55) 7663–767. (2022)reponame:Repositorio Institucional Abierto (UTN)instname:Universidad Tecnológica NacionalengengInternacionalinfo:eu-repo/semantics/openAccess2024-04-03T20:15:26Zhttp://creativecommons.org/licenses/by-nc-nd/4.0/Attribution-NonCommercial-NoDerivatives 4.0 Internacional.2026-09-24T12:45:44Zoai:ria.utn.edu.ar:20.500.12272/10287instacron:UTNInstitucionalhttp://ria.utn.edu.ar/Universidad públicaNo correspondehttp://ria.utn.edu.ar/oaigestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:a2026-09-24 12:45:45.781Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacionalfalse
dc.title.none.fl_str_mv Supernucleation dominates lignin/poly(ethylene oxide) rystallization kinetics
title Supernucleation dominates lignin/poly(ethylene oxide) rystallization kinetics
spellingShingle Supernucleation dominates lignin/poly(ethylene oxide) rystallization kinetics
Taverna, María E.
Lignin
Crystallization
Poly(ethylene oxide)
title_short Supernucleation dominates lignin/poly(ethylene oxide) rystallization kinetics
title_full Supernucleation dominates lignin/poly(ethylene oxide) rystallization kinetics
title_fullStr Supernucleation dominates lignin/poly(ethylene oxide) rystallization kinetics
title_full_unstemmed Supernucleation dominates lignin/poly(ethylene oxide) rystallization kinetics
title_sort Supernucleation dominates lignin/poly(ethylene oxide) rystallization kinetics
dc.creator.none.fl_str_mv Taverna, María E.
Altorbaq, Abdullah S.
Kumar, Sanat K.
Olmedo Martínez, Jorge L.
Busatto, Carlos Alberto
Zubitur, Manuela
Mugica, Agurtzane
Nicolau, Verónica V.
Estenoz, Diana
Müller, Alejandro J.
author Taverna, María E.
author_facet Taverna, María E.
Altorbaq, Abdullah S.
Kumar, Sanat K.
Olmedo Martínez, Jorge L.
Busatto, Carlos Alberto
Zubitur, Manuela
Mugica, Agurtzane
Nicolau, Verónica V.
Estenoz, Diana
Müller, Alejandro J.
author_role author
author2 Altorbaq, Abdullah S.
Kumar, Sanat K.
Olmedo Martínez, Jorge L.
Busatto, Carlos Alberto
Zubitur, Manuela
Mugica, Agurtzane
Nicolau, Verónica V.
Estenoz, Diana
Müller, Alejandro J.
author2_role author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Lignin
Crystallization
Poly(ethylene oxide)
topic Lignin
Crystallization
Poly(ethylene oxide)
dc.description.none.fl_txt_mv The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed welldispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/ PEO) in the brush-controlled regime.
Fil: Taverna, María E. UNL - CONICET. INTEC - Universidad Tecnológica Nacional. Facultad Regional San Francisco. Departamento de Ingeniería Química, Grupo UTN GPol; Argentina.
Fil: Altorbaq, Abdullah S. Columbia University. Department of Chemical Engineering; USA
Fil: Kumar, Sanat K. Columbia University. Department of Chemical Engineering; USA.
Fil: Olmedo-Martínez, Jorge L. Basque Foundation for Science. IKERBASQUE; España.
Fil: Busatto, Carlos Alberto. UNL - CONICET. INTEC; Argentina
Fil: Zubitur, Manuela. University of the Basque Country UPV/EHU. Chemical and Environmental Engineering Department; España.
Fil: Mugica, Agurtzane. University of the Basque Country UPV/EHU. POLYMAT; España.
Fil: Nicolau, Verónica V. Universidad Tecnológica Nacional. Facultad Regional San Francisco. Departamento de Ingeniería Química, Grupo UTN GPol - CONICET; Argentina.
Fil: Estenoz, Diana. UNL - CONICET. INTEC; Argentina.
Fil: Alejandro J. Müller. Basque Foundation for Science. IKERBASQUE; España.
Peer Reviewed
description The effect of lignin nanoparticles (LNPs) on the crystallization kinetics of poly(ethylene oxide) (PEO) is examined. Lignin from spruce and ionic isolation was used to prepare LNPs with a number-averaged diameter of 85 nm (with a relatively large polydispersity) by an ultrasonication method. PEO-based nanocomposites with four different LNP contents (5, 10, 15, and 20 wt %) were prepared and subject to isothermal and nonisothermal crystallization protocols in a series of experiments. Scanning electron microscopy (SEM) images showed welldispersed LNPs in the crystallized PEO matrix. The incorporation of LNPs exponentially increases nucleation density at moderate loadings, with this trend apparently saturating at higher loadings. However, the spherulitic growth rate decreases monotonically with LNP loading. This is attributed to the substantial PEO/LNP affinity, which impacts chain diffusion and induces supernucleation effect (with efficiencies in the order of 200%), but leads to slower growth rates. The overall crystallization kinetics, measured by the DSC, shows faster nanocomposite crystallization rates relative to the neat PEO at all LNP contents examined. This indicates that the supernucleation effect of LNPs dominates over the decrease in the growth rates, although its influence slightly decreases as the LNP content increases. The strong hydrogen-bonded interactions between the LNPs and the PEO are thus reminiscent of confinement effects found in polymer-grafted NP nanocomposites (e.g., PEO-g-SiO2/ PEO) in the brush-controlled regime.
publishDate 2022
dc.date.none.fl_str_mv 2022-08
2024-04-03T20:15:26Z
2024-04-03T20:15:26Z
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv Macromolecules 2022, 55, 17, 7663–7673 Publication Date:August 26, 2022 https://doi.org/10.1021/acs.macromol.2c00925
15205835
https://pubs.acs.org/doi/10.1021/acs.macromol.2c00925
http://hdl.handle.net/20.500.12272/10287
identifier_str_mv Macromolecules 2022, 55, 17, 7663–7673 Publication Date:August 26, 2022 https://doi.org/10.1021/acs.macromol.2c00925
15205835
url https://pubs.acs.org/doi/10.1021/acs.macromol.2c00925
http://hdl.handle.net/20.500.12272/10287
dc.language.none.fl_str_mv eng
eng
language eng
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
2024-04-03T20:15:26Z
http://creativecommons.org/licenses/by-nc-nd/4.0/
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
.
eu_rights_str_mv openAccess
rights_invalid_str_mv 2024-04-03T20:15:26Z
http://creativecommons.org/licenses/by-nc-nd/4.0/
Attribution-NonCommercial-NoDerivatives 4.0 Internacional
.
dc.format.none.fl_str_mv pdf
application/pdf
dc.coverage.none.fl_str_mv Internacional
dc.source.none.fl_str_mv Macromolecules 2022 (55) 7663–767. (2022)
reponame:Repositorio Institucional Abierto (UTN)
instname:Universidad Tecnológica Nacional
reponame_str Repositorio Institucional Abierto (UTN)
collection Repositorio Institucional Abierto (UTN)
instname_str Universidad Tecnológica Nacional
repository.name.fl_str_mv Repositorio Institucional Abierto (UTN) - Universidad Tecnológica Nacional
repository.mail.fl_str_mv gestionria@rec.utn.edu.ar; fsuarez@rec.utn.edu.ar
_version_ 1877230908803645440
score 13.24418

Publicaciones similares